CN1850878A - Method for preparing carbon nano tube epoxy resin curing agent - Google Patents
Method for preparing carbon nano tube epoxy resin curing agent Download PDFInfo
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- CN1850878A CN1850878A CN 200610026000 CN200610026000A CN1850878A CN 1850878 A CN1850878 A CN 1850878A CN 200610026000 CN200610026000 CN 200610026000 CN 200610026000 A CN200610026000 A CN 200610026000A CN 1850878 A CN1850878 A CN 1850878A
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Abstract
The invention discloses a manufacture method for a new type carbon nanometer tube epoxy resin curing agent that includes the following steps: taking ultrasound for 10-120min for carbon nanometer by vitriol/nitric acid in room temperature, and the reacting temperature is 50-170 degree centigrade, and reacting time is 10-120min to gain carboxylation carbon nanometer tube; adding protochloride sulfoxide to take acyl chloride reaction, and the production dissolving in N, N'-dimethyl formamide solvent, the reaction temperature is 60-200 degree centigrade, adding aromatic amido group compound to make aromatic amido group carbon nanometer tube. The benefit of the invention is that the mechanical property and thermal stability could be improved.
Description
Technical field
The present invention relates to a kind of preparation method of solidifying agent, particularly relate to a kind of preparation method of carbon nano tube epoxy resin curing agent.
Background technology
Carbon nanotube has unique atomic structure, very high specific surface area, and performances such as good electricity, magnetics, mechanics, therefore in scientific research and practical application, carbon nanotube has broad application prospects in various fields.
Resins, epoxy is a kind of thermoset oligopolymer, poor performance.Except that as the stablizer of polyvinyl chloride etc., there is not direct use value.But after it and solidifying agent are cured reaction and form the three-dimensional crosslinked network structure, then present the performance of a series of excellences.So the chemical reaction performance of solidifying agent and Resins, epoxy is basis, core that Resins, epoxy is used.Behavior and the performance of cured article of Resins, epoxy in solidification process depends on influencing each other and rationally cooperate between curing agents and it and the resin to a great extent, and these depend on the molecular structure of solidifying agent, therefore, being applied in of Resins, epoxy of research is exactly the problem of studying epoxy curing agent in a way.
In epoxy resin composite material, an important factor is the hardness of balance solidifying agent degree of crosslinking and Resins, epoxy.Usually the degree of crosslinking raising will cause impact capacity to descend.Carbon nanotube is the highest nano material of intensity, if carbon nanotube can be used as epoxy curing agent, the mechanical property of epoxy resin composite material will be significantly increased so.
J.Zhu (Adv.Funct.Mater.2004,14, No.7, July) and Man-LungSham (Carbon 2005, in press) carbon nano tube surface is inserted alicyclic and the fatty amine based compound, be used for epoxy curing agent and come cured epoxy resin, improve the mechanical property of Resins, epoxy.But add the thermotolerance variation that alicyclic or aliphatics amido solidifying agent can make Resins, epoxy in Resins, epoxy, though therefore alicyclic and adding aliphatics amido carbon nano tube improves the mechanical property of Resins, epoxy, thermostability descends.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of carbon nano tube epoxy resin curing agent, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of carbon nano tube epoxy resin curing agent comprises the steps:
(1) preparation of carboxylic carbon nano-tube: carbon nanotube is added in the reaction vessel, with volume ratio 3: 1 the at room temperature ultrasonic 10～120min of sulfuric acid/nitric acid, temperature of reaction is 50～170 ℃, reaction times is 10～120min, extremely neutral with deionized water wash, under 50 ℃, the vacuum drying oven drying obtains carboxylic carbon nano-tube;
(2) chloride is handled: carboxylated carbon nanotube is dissolved in N, in N '-dimethyl formamide solution, and ultrasonic 10～120min under the room temperature, in temperature of reaction is 40～120 ℃, reaction times is under 12～120h condition, adds sulfur oxychloride and carries out acyl chloride reaction, and product is through N, N '-dimethyl formamide, methanol wash, the vacuum drying oven drying, products therefrom is dissolved in N, in N '-dimethyl formamide solution, in temperature of reaction is 60～200 ℃, and the reaction times is under 12～120h condition, adds the aromatic amine based compound, preparation aromatic series amido carbon nano tube, product is through N, N '-dimethyl formamide, tetrahydrofuran (THF), absolute ethanol washing, vacuum-drying.
As optimized technical scheme: comprise the steps:
(1) preparation of carboxylic carbon nano-tube: carbon nanotube is added in the reaction vessel, is 3: 1 the at room temperature ultrasonic 20～30min of sulfuric acid/nitric acid with volume ratio, and temperature of reaction is 100～140 ℃, and the reaction times is 20～40min; To neutral, under 50 ℃, the vacuum drying oven drying obtains carboxylic carbon nano-tube with deionized water wash;
(2) chloride is handled: carboxylated carbon nanotube is dissolved in N, in N '-dimethyl formamide solution, and ultrasonic 20～30min under the room temperature, in temperature of reaction is 50～80 ℃, reaction times is under 24～36h condition, adds sulfur oxychloride and carries out acyl chloride reaction, and product is through N, N '-dimethyl formamide, methanol wash, the vacuum drying oven drying, products therefrom is dissolved in N, in N '-dimethyl formamide solution, in temperature of reaction is 80～120 ℃, and the reaction times is under 24～60h condition, adds the aromatic amine based compound, preparation aromatic series amido carbon nano tube, product is through N, N '-dimethyl formamide, tetrahydrofuran (THF), absolute ethanol washing, vacuum-drying.
Described aromatic amine based compound is one or more in m-xylene diamine, mphenylenediamine, two amido ditans and the two amido sulfobenzides.
Described carbon nanotube is many walls or Single Walled Carbon Nanotube.
The present invention is a raw material with single wall or multi-walled carbon nano-tubes,, uses the nitration mixture oxide treatment under certain condition, makes its surface insert functional groups such as carboxyl, hydroxyl.The aminated of carbon nanotube passes through at a certain temperature with the first sulfur oxychloride (SOCl of passing through of the carbon nanotube of nitration mixture oxide treatment
2) carry out chloride, the product that makes carries out aminated reaction with aromatic amine based compound such as m-xylene diamine, mphenylenediamine, two amido ditans and two amido sulfobenzides etc. under certain condition, preparation aromatic series amido carbon nano tube epoxy curing agent.
Reaction process is as follows:
The chemically modified of carbon nanotube carboxyl:
The chemically modified of carbon nanotube aromatic series amido:
SOCl
2Acyl chloride reaction:
The invention has the beneficial effects as follows: connect aromatic amine based compound epoxy curing agent in carbon nano tube surface, improved mechanical property, the thermostability of Resins, epoxy.Improved dispersiveness and the content of carbon nanotube in Resins, epoxy, the interface of improving carbon nanotube and Resins, epoxy.
Description of drawings
The infrared spectrogram of Fig. 1 embodiment 1 gained carboxylic carbon nano-tube
The infrared spectrogram of Fig. 2 embodiment 1 gained aromatic series amido carbon nano tube epoxy curing agent
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1:
With 3g purity is that 95% multi-walled carbon nano-tubes joins in the 500ml there-necked flask that has whipping appts, adding volume ratio then is 3: 1 the vitriol oil and the mixture of concentrated nitric acid, ultrasonic 30min, at 120 ℃, the reaction times is oxide/carbon nanometer tube under the 30min condition.The 1g carboxylic carbon nano-tube is dissolved in N, and ultrasonic 30min among the N '-dimethyl formamide (DMF) adds 30ml sulfur oxychloride (SOCl
2), temperature of reaction is 50 ℃, the reaction times is to carry out acyl chloride reaction under the 24h condition.Product is through DMF, methanol wash, 50 ℃ of vacuum drying oven dryings.Get 0.5g chloride carbon nanotube and be dissolved among the DMF ultrasonic 30min.Add 1g N, N '-two amido sulfobenzide is in N, and in N '-dimethyl formamide (DMF) solution, temperature of reaction is 80 ℃, and the reaction times is under the 60h condition, and aminated reaction is carried out in nitrogen protection, preparation aromatic series amido carbon nano tube epoxy curing agent.Reaction equation is as follows:
Embodiment 2:
Prepare carboxylated multi-walled carbon nano-tubes by embodiment 1 described method.The 1g carboxylic carbon nano-tube is dissolved in ultrasonic 10min among the DMF, adds 30mlSOCl
2, temperature of reaction is 120 ℃, the reaction times is to carry out acyl chloride reaction under the 12h condition.Product is through DMF, methanol wash, 50 ℃ of vacuum drying oven dryings.Get 0.5g chloride carbon nanotube and be dissolved among the DMF ultrasonic 30min.Add 1g N, N '-two amido ditan is in DMF solution, and temperature of reaction is 200 ℃, and the reaction times is under the 12h condition, and aminated reaction is carried out in nitrogen protection, preparation aromatic series amido carbon nano tube epoxy curing agent.Reaction equation is as follows:
Embodiment 3:
Prepare carboxylated multi-walled carbon nano-tubes by embodiment 1 described method.The 1g carboxylic carbon nano-tube is dissolved in ultrasonic 120min among the DMF, adds 30mlSOCl
2, temperature of reaction is 40 ℃, the reaction times is to carry out acyl chloride reaction under the 120h condition.Product is through DMF, methanol wash, 50 ℃ of vacuum drying oven dryings.Get 0.5g chloride carbon nanotube and be dissolved among the DMF ultrasonic 30min.Add the 1g mphenylenediamine in DMF solution, temperature of reaction is 60 ℃, and the reaction times is under the 120h condition, and aminated reaction is carried out in nitrogen protection, preparation aromatic series amido carbon nano tube epoxy curing agent.Reaction equation is as follows:
Claims (4)
1, a kind of preparation method of carbon nano tube epoxy resin curing agent is characterized in that comprising the steps:
(1) preparation of carboxylic carbon nano-tube: carbon nanotube is added in the reaction vessel, with volume ratio 3: 1 the at room temperature ultrasonic 10～120min of sulfuric acid/nitric acid, temperature of reaction is 50～170 ℃, reaction times is 10～120min, extremely neutral with deionized water wash, under 50 ℃, the vacuum drying oven drying obtains carboxylic carbon nano-tube;
(2) chloride is handled: carboxylated carbon nanotube is dissolved in N, in N '-dimethyl formamide solution, and ultrasonic 10～120min under the room temperature, in temperature of reaction is 40～120 ℃, reaction times is under 12～120h condition, adds sulfur oxychloride and carries out acyl chloride reaction, and product is through N, N '-dimethyl formamide, methanol wash, the vacuum drying oven drying, products therefrom is dissolved in N, in N '-dimethyl formamide solution, in temperature of reaction is 60～200 ℃, and the reaction times is under 12～120h condition, adds the aromatic amine based compound, preparation aromatic series amido carbon nano tube, product is through N, N '-dimethyl formamide, tetrahydrofuran (THF), absolute ethanol washing, vacuum-drying.
2, preparation method according to claim 1 is characterized in that comprising the steps:
(1) preparation of carboxylic carbon nano-tube: carbon nanotube is added in the reaction vessel, is 3: 1 the at room temperature ultrasonic 20～30min of sulfuric acid/nitric acid with volume ratio, and temperature of reaction is 100～140 ℃, and the reaction times is 20～40min; To neutral, under 50 ℃, the vacuum drying oven drying obtains carboxylic carbon nano-tube with deionized water wash;
(2) chloride is handled: carboxylated carbon nanotube is dissolved in N, in N '-dimethyl formamide solution, and ultrasonic 20～30min under the room temperature, in temperature of reaction is 50～80 ℃, reaction times is under 24～36h condition, adds sulfur oxychloride and carries out acyl chloride reaction, and product is through N, N '-dimethyl formamide, methanol wash, the vacuum drying oven drying, products therefrom is dissolved in N, in N '-dimethyl formamide solution, in temperature of reaction is 80～120 ℃, and the reaction times is under 24～60h condition, adds the aromatic amine based compound, preparation aromatic series amido carbon nano tube, product is through N, N '-dimethyl formamide, tetrahydrofuran (THF), absolute ethanol washing, vacuum-drying.
3, preparation method according to claim 1 and 2 is characterized in that: described aromatic amine based compound is one or more in m-xylene diamine, mphenylenediamine, two amido ditans and the two amido sulfobenzides.
4, preparation method according to claim 1 and 2 is characterized in that: described carbon nanotube is many walls or Single Walled Carbon Nanotube.
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| CN 200610026000 CN1850878A (en) | 2006-04-25 | 2006-04-25 | Method for preparing carbon nano tube epoxy resin curing agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407620B (en) * | 2007-10-11 | 2011-05-25 | 同济大学 | High performance epoxy resins composite material and preparation thereof |
| WO2015135196A1 (en) * | 2014-03-14 | 2015-09-17 | 绵阳鸿琪新材料科技有限公司 | Antistatic polyether sulfone composite material and preparation method therefor |
-
2006
- 2006-04-25 CN CN 200610026000 patent/CN1850878A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407620B (en) * | 2007-10-11 | 2011-05-25 | 同济大学 | High performance epoxy resins composite material and preparation thereof |
| WO2015135196A1 (en) * | 2014-03-14 | 2015-09-17 | 绵阳鸿琪新材料科技有限公司 | Antistatic polyether sulfone composite material and preparation method therefor |
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